Light sensitive diazotype material and diazonium compounds therefor



Aug. 20, 1968 A. J. J. HENDRICKX LIGHT SENSITIVE DIAZOTYPB MATERIAL ANDDIAZONI UM COMPOUNDS THEREFOR Filed Dec. 31, 1964 2 Sheets-Sheet 2ATTORNEY United States 3,397,985 LIGHT SENSITIVE DIAZOTYPE MATERIAL ANDDIAZONIUM COMPOUNDS THEREFOR Andreas Joseph Johannes Hendrickx, Venlo,Netherlands, assignor to Van der Grinten N.V., Northern Limburg,Netherlands Filed Dec. 31, 1964, Ser. No. 422,693 Claims priority,application Netherlands, June 1, 1964, 6406149 9 Claims. (CI. 9691)ABSTRACT OF THE DISCLOSURE The invention relates to diazotype materialcontaining a benzene diazonium salt of a new type and more particularlyto one-component diazotype material which is very suitable fordevelopment according to the so-called thin layer method with weaklyacid 'buifered developing liquids commonly used in the one-componentdiazotype process.

In this specification reference is made to the structural chemicalformula of compounds. These formulae are set out in the accompanyingdrawings and the references herein are to the figures of these drawings.

Diazotype materials "can be distinguished into: onecomponent diazotypematerials, which are developed with the aid of a liquid containing anazo-cou'pling component', two-component diazotype materials, which aredeveloped with the aid of gaseous alkali (ammonia); heat-developablediazotype materials; planographic printing plates sensitized with diazocompounds.

One-component diazotype material is usually developed by spreading(after imagewise exposure) a thin layer (4-12 g./m. of an aqueousdeveloping liquid on the sensitized surface (and also on thenon-sensitized surface, if desired).

The developing liquids commonly used in the one-component diazotypeprocess are usually distinguished into alkaline liquids having a pHabove 7 and buffered weakly acid liquids the pH of which is between 5.5and 7. Because of their high keeping quality the weakly acid developersare to be preferred to the alkaline developers. In fact, in diazotypedevelopers phloroglucinol, which in alkaline medium is readily oxidizedby the oxygen from the air, is practically always used as azo-couplingcomponent. Developers, both alkaline and buifered Weakly aciddevelopers, which contain phloroglucinol as 2120- coupling component,often in combination with a quantity of resorcinol, are used on a largescale in practice.

In diazotype materials which can be developed with a weakly acidbulfered developer, various diazo compounds derived from hydroquinonedialkyl and diaralkyl ethers and having high coupling activity areemployed. Groups of such diazo compounds are: those with the generalatent O 3,397,985 Patented Aug. 20, 1968 formula according to FIGURE 1,in which X is an anion, R and R are alkyl or aralkyl groups, R standsfor a substituted or a non-substituted alkyl, aralkyl, aryl, alkoxy,aralkoxy, aryloxy, a substituted amidocarbonyl or a substituted amidoradical, and R for a hydrogen atom or an alkyl group or is an alkyl oracyl group which forms a heterocyclic ring With N-COR (See: Britishpatent specifications Nos. 347,430, 615,774, 539,031, 510,874, 449,341,520,304, 620,038, 538,869 and 643,- 309); those with the general formulaaccording to FIGURE -2, in which R, stands for a hydrogen atom, analkyl, aralkyl, or aryl group '(see: U.S. patent specification No.2,665,985); those with the general formula according to FIGURE 3, inwhich R stands for a substituted or a non-substituted alkyl, aralkyl, oraryl group (see: 'Fiat Final Report 813, pages 137 and 138, Dutch patentspecification No. 51,536, British patent specification No. 759,045 andGerman patent specification No. 896,591); and those with the generalformula according to FIGURE 4, in which R stands for hydrogen, anacetylamino group, a light alkyl or alkoxy group (see: British patentspecification No. 471,614).

The diazo compounds according to the formulae of FIGURES 14 uponexposure yield a somewhat stained photo-decomposition product, so thatcopies made on a diazotype material sensitized with such a compound showa stained background. When the support of the diazotype material iswhite paper, the background of the copies instead of being bright white,shows a somewhat dingy stain; when the support is transparent, thecopieseven if the azo-dyestuif image has high absorption for ultravioletradiation-are not very suitable as intermediate originals for makingfurther copies on diazotype material, because the presence of thestained photo-decomposition product in the image-free portions of theintermediate original decreases its transparency to the ultra-violetcopying radiation, and thus necessitates a longer exposure time whenfurther copies are to be made.

Dutch patent application No. 288,469, not previously published,describes diazotype material which contains a diazo compound of thegeneral formula according to FIGURE 5, in which X is an anion, R standsfor an alkyl, branched alkyl, cycloalkyl, or aralkyl group, CO-R for anacyl radical, R for a substituent from the group formed by acylamido,alkylsulfonamido, aralkylsulfonamido, arylsulfonamido, and triazinylradicals, and R for an alkyl, branched alkyl, cycloalkyl, aralkyl, oraryl radical.

Dutch patent application No. 295,561, not previously published,described diazotype material which contains a diazo compound of thegeneral formul aaccording to FIGURE 6, in which Xis an anion, R standsfor an alkyl, branched alkyl, cycloalkyl, or aralkyl group, COR for anacyl radical, R for a saturated or nonsaturated organic radical,including the cyano radical, and R for an alkyl, branched alkyl,cycloalkyl, aralkyl, or aryl radical.

The diazotype materials according to the Dutch patent applications Nos.288,469 and 295,561 have a higher developing speed than diazotypematerial which has been sensitized with a similar diazo compound,derived from hydroquinone, according to the formulae of FIGURES 1-4, andthey are often more light-sensitive as Well, particularly when R is asmall alkyl group.

The present invention relates to diazotype material characterized inthat it contains a diazo compound of the-general 'formula according toFIGURE 7, in which X is an anion, R stands for an alkyl (Le, anon-branched ir branched alkyl), alkenyl, cycloalkyl, aralkyl, or arylgroup, and Y for a substituent from the group formed by acylamino,etherified mercapto, dihydrotriazinyl, and substituted ornon-substituted phenyl groups.

In this connection by acylamino is to be understood that radical inwhich R; stands for an organic radical and R for a hydrogen atom, analkyl or aralkyl group, or for an alkyl or acyl radical which forms aheterocyclic ring with NCOR As compared with diazotype material whichhas been sensitized with a similar diazo compound derived fromhydroquinone, the diazotype material according to the invention showshigher light-sensitivity, while moreover it bleaches out brighter.

As compared with the comparable diazotype materials described in theDutch patent application Nos. 288,469 and 295,561, the diazotypematerial according to the invention is a little more light-sensitive andas a rule has better keeping quality. Besides, it bleaches out brighter.

The fact that the diazotype material according to the invention bleachesout bright is manifest when the material, while being printed, has ahigh moisture content, for instance because it has been kept in a humidatmosphere for some hours. Thus copies made of diazotype paper accordingto the invention, which has been left unpacked, e.g. for an hour in anofiice room having a temperature of 20 C. and a relatively humidity of75% before the copies were made, show a much whiter background thancopies on diazotype materials sensitized with diazo compounds accordingto the formulae of FIGURES 1-6 and stored under the same conditions.

The diazotype material according to the invention is preferablyone-component diazotype material. Upon development with weaky acidphloroglucinol developers it yields properly developed copies withstrong red to very dark-brown azo-dyestufi images. (Of course,one-component diazotype material according to the invention can bedeveloped with weakly alkaline developing liquids; copies also showingstrong, somewhat lighter, red to brown azodyestufis are then obtained).The diazotype material according to the invention may also beheatdevelopable diazotype material.

Whatever may be the composition of the F(nxecoing Whatever may be thecomposition of the material and the method of development, if theazo-dyestutfs formed upon development are sufliciently oleophilic and ifthe support has the appropriate constitution the copies can be used as aplanographic printing form.

Diazo compounds which can be used in the diazotype material according tothe invention are:

4-diazo-2-methoxy-5-pyrrolidon 2)yl( 1 )-N-acetylaniline4-diazo-2-ethoxy-5-pyrrolidon(2) yl( 1 )-N-ethoxycarb onylaniline4-diazo-2-benzyloxy-5 -pyrrolidon( 2)yl( l -N-butyrylaniline 4-diazo-2-(4'-ch1orobenzyl oxy-S-pyrrolidon 2) yl( 1)- N-acetylaniline4-diazo-2-methoXy-5-pyrrolid0n 2) yl( 1 )-N-chloroacetylaniline4-diazo-2- 2'-ethylbut) oxy-S-pyrrolidon (2) yl( 1 )-N-phenacetylaniline 4-diazo-2-methoXy-5 -pyrro1idon(2 yl 1 )-N-benzoylaniline S-methoxy-2,4-di-pyrrolidon (2 yl 1)-diazobenzene4-diazo2-methoxy-5-pyrrolidon(2)yl(1)-N-methyl- N-benzoylaniline4-diazo-2-ethoxy-5-pyrrolidon (2 yl 1 )-N- benzoylaniline4-diazo-2-n-propoxy-5-pyrrolidon(2 yl( l -N- benzoylaniline4-diazo-2-n-butoxy-5-pyrrolidon(2)yl(1)-N- benzoylaniline4-diazo-2-isoamyloxy-S-pyrrolidon( 2 yl( 1 )-N- benzoylaniline Y4-diazo-2- 2-hydroxyethyl oxy-S-pyrrolidon (2 yl( 1)- N-benzoylaniline4-diazo-2-ethoxyethoxy-5-pyrrolidon (2 )yl( 1 )-N- benzoylaniline4-diazo-2-( 2'-diethylaminoeth) oxy-S-pyrrolidon (2 yl( l)-N-benzoylaniline 4-diazo-2- 4'-chlorophen oxy-S-pyrrolidon (2 yl( 1N-benzoylaniline 4-diazo-2-allyloxy-S-pyrrolidbn( 2)yl( l -N-benzoylaniline 4-diazo-2-cyclopentoxy-pyrrolidon 2 )yl( l )-N-benzoylaniline bis-N,N-4'-diazo-2'-methoxy-5- pyrrolidon 2 yl( 1)-phenyl urea 1- (4-diazo-2'methoxy-5 -pyrrolidon 2 yl 1 phenyl -4 [2]-amino-2- [4] -imino-6-rnethyl- 1H,2H[1H,4H] 1,3,5 -triazine4-diazo-2-methoxy-5 -pyrrolidon (2 yl( 1)- phenylthiomethyl ether4-diazo-2-ethoxy-S-pyrrolidon (2 yl( 1 phenylthiomethyl ether4-diazo-2-n-propoxy-S-pyrrolidon (2 )yl( 1 phenylthiomethyl ether4-diazo-2-n-but0xy-S-pyrrolidon( 2 yl l phenylthiomethyl ether4-diazo-2-methoxy-S-pyrrolidon 2 yl( l phenylthioethyl ether4-diazo-2-ethoxy-5-pyrrolidon( 2 yl( l )-phenylthioethyl ether4-diazo-2-n-propoxy-S-pyrrolidon 2 yl 1)- phenylthioethyl ether4-diazo-2-ally1oxy-5 -pyr-rolidon (2 )yl( l phenylthioethyl ether4-diazo-2-n-butoxy-5-pyrrolidon (2 yl( 1)- phenylthioethyl ether4-diazo-2- (4'-chlorophen oxy-S -pyrrolidon 2) yl( 1 phenylthioethylether 4-diazo-2-cyclopentoxy-S-pyrrolidon(2)yl(1)- phenylthioethyl ether4-diazo-2-methoxy-ipyrrolidon(2) yl( l phenylthiobutyl ether4-diazo-2-(2'-ethylbut) oxy-S-pyrrolidon (2 yl( lphenylthiocar-boxymethyl ether 4-diazo-2-benzyloxy-S-pyrrolidon (2)yl(1)- phenylthiobenzyl ether ethanedithiol-(1,2)-bis(4-diazo-2-meth0xy-5pyrrolidon (2 yl( 1 )-phenyl ether 4-diazo-2-methoxy-5-pyrrolidon (2 yl(l )-pheny1thiop-tolyl ether 4-diazo-2-ethoxy-5 -pyrrolid on 2 yl( 1-phenylthiop-tolyl ether 4-diazo-2-n-propoxy-5-pyrrolidon 2) yl 1-phenylthiop-tolyl ether 4-diazo-2-n-butoxy-5-pyrrolidon (2 yl( lphenylthio-p-tolyl ether 4-diazo-2- (4'-chlorophen oxy-S-pyrrolidon 2yl( 1 phenylthio-ptolyl ether 4-diazo-2-methoxy-S-pyrrolidon 2) yl 1.-diphenyl 4-diazo-2-ethoxy-5-pyrrolidon (2 )yl( l )-diphenyl4-diazo-2-n-propoxy-S-pyrrolidon (2 )yl( l)- diphenyl4-diazo-2-n-butoXy-5 -pyrroli don 2) yl 1 diphenyl4-diazo-2-cyclopentoxy-S-pyrrolidon (2 yl 1)- diphenyl4-diazo-2,4'-dimethoxy-5-pyrrolidon 2 yl( 1)- diphenyl4-diazo-2-n-butoxy-4-methoxy-5-pyrrolidon(2 yl 1 diphenyl.

The diazo compounds are used as diazonium salts, for instance aschlorides or sulfates, or as diazonium metal double salts, such as thezinc chloride double salt, the manganese chloride double salt, and thestannic chloride double salt, or as borofluorides. They can be appliedseparately, mixed together, or in admixture with diazo compounds ofother types. It is obvious that, when mixtures are used, the effect ofthe new diazo compounds will be smaller according as a larger quantityof the other compound(s) is used.

Although the diazo compounds according to the invention have highcoupling activity and good light-sensitivity, moreover bleach out whileforming practically colourless photo-decomposition products, and yieldhighcontrast azo-dyestuffs with the conventional azocoupling components,such as phloroglucinol and resorcinol, nevertheless there aredifferences in qualities and accessibility between the various diazocompounds.

Because of their ready accessibility, their comparatively very highcoupling activity, and their relatively high stability, the diazocompounds having a benzoylamino or an etherified mercapto group inpara-position relative to the diazo group are preferred. Diazotypematerials which have good keeping quality, develop very rapidly, and arereasonably inexpensive can be prepared with these diazo compounds.

Very useful compounds are, for instance, those of the general formulaaccording to FIGURE 8 in Which R represents a non-branched alkyl grouphaving up to 5 carbon atoms and X represents an anion.

Particularly valuable diazo compounds are those with an alkyl, aralkyl,or arylthio group in para-position and more especially those of thegeneral formula according to FIGURE 9, in which R represents anon-branched alkyl group having up to 5 carbon atoms, R represents anon-branched alkyl group having up to 4 carbon atoms or a substituted ornon-substituted benzyl or phenyl group, and X represents an anion.

Diazotype material sensitized therewith has. higher light-sensitivitythan diazotype material according to the invention containing a diazocompound with another substituent in para-position.

In the diazotype material according to the invention, the support to beused may be paper, printing-plate paper, tracing paper, transparentizedpaper, linen, tracing linen, synthetic paper, film material, such asfilms of cellulose acetate and polyester, metal, e.g. planographicprinting plates of aluminium.

Furthermore the diazotype material according to the invention maycontain the additions commonly used in the diazotype process, e.g.acids, such as citric acid, tartaric acid, and boric acid; stabilizers,such as benzene and naphthalene sulfonic acids and their water-solublesalts, e.g. sodium napthalene 1,3,6-trisulfonate; metal salts, such aszinc chloride, magnesium chloride, nickel sulfate, and alum;surface-improving substances, such as finely divided silica (colloidalor non-colloidal), aluminium oxide, barium sulfate, rice starch, etc.;binders, such as gelatin, gum arabic, cellulose ethers, starchderivatives, polyvinyl alcohol; dispersions of synthetic resins, such asdispersions of polyvinyl acetate in aqueous media containing cationic,non-ionic or anionic dispersing agents.

The phloroglucinol developers which are used in the one-componentdiazotype process often vary as to their composition and acidity. Belowthree weakly acid phloroglucinol developers employed in practice aredescribed. These developers will be used for development in thefollowing examples.

Developer A is a solution of:

Phloroglucinol g .4 Acetoacetanilide 0.1 2-ethyl-1-hexanol sulfateTergitol 08 (from Union Carbide & Carbon Corp., New York 17, U.S.A.;

Tergitol is a registered trademark) ml 3 Beet sugar g 15 Benzoic acid g2.5 Sodium benzoate g 14 Sodium formate g 135 in 1000 ml. of water.

The pH of this liquid is approximately 5.8.

Developer B is a solution of:

Phloroglucinol 6.5 Resorcinol 4 Thiourea 10 Sodium butylnaphthalenesulfonate Sorbit P (from Geigy Chem. Corp. Ardsley, N.Y., U.S.A.; the

word Sorbit is a registered trademark) 2 Sodium formate 14 Sodiumbenzoate 22 Trisodium citrate (2 aq.) 49 Citric acid 1.2

in 1000 ml. of water.

The pH of this liquid is 6.5.

Developer C is a solution of:

Phloroglucinol g- 5 Resorcinol g 1 Dipotassium phosphate 3 Tergitol 08ml 3 Maleic anhydride g 52 Potassium hydroxide solution (13.5 N) ml 75in 1000 ml. of Water.

The pH of this liquid is 6.9.

In addition to phloroglucinol (and in addition to, or instead of,resorcinol), the weakly acid buffered developers may also contain otherazo-coupling components having high coupling activity, e.g. 2,3dihydroxynaphthalene, and acetoacetanilide. The following examples willserve to illustrate the invention:

Example I Three sensitizing liquids are prepared: (A) A liquidcontaining:

G. 4-benzoylamino 2 pyrrolidon(2)yl(1)-5-methoxybenzene diazoniumchloride, zinc chloride double salt 16.6 Tartaric acid 5 Saponin 3 in1000 ml. of water.

(B) A similar liquid to that mentioned under (A), but containing,instead of the 4-benzoylamino-2-pyrrolidon- (2)yl(1)-5- methoxybenzenediazonium salt, and equimolar quantity of4-benzoylamino-2-N-methyl-N-acetylamino-Sanethoxy benzene diazoniumchloride, zinc chloride double salt.

(C) A similar liquid to that mentioned under (A), but containing,instead of the said diazonium salt, an equimolar quantity of4-benzoylamino-2,S-dimethoxybenzene diazonium chloride, zinc chloridedouble salt.

With each of these liquids a sheet of white base paper of weight g./m.and suitable for the diazotype process is sensitized. Aftersensitization the three sheets are dried. Each sheet containsapproximately 0.40 millimol of diazo compound per m A strip of eachsheet is imagewise exposed underneath a transparent ink drawing for thetime required to bleach out, on the strip of sheet (A), all the diazocompound underneath the image-free portions of the original. After this,the strips are developed with developer (A).

Strip (A) shows a violet-brown image on a bright white background. Strip(B) shows a dark brown image on a somewhat foggy background, and strip(C) shows a black image on a heavy violet-grey background.

A second strip of the sheets (A), (B) and (C), screened from the light,is kept for an hour in a room having a relative humidity of 75% and atemperature of approximately 20 C. The strips are then fed, togetherwith a transparent ink rdrawing, through a continuously operatingexposure apparatus for the diazotype process comprising an exposurecylinder of glass which has a surface temperature of approximately 60 C.and in which a high-pressure mercury vapour lamp is mounted, with such aspeed that, on strip (C), all the diazo compound underneath theimage-free portions of the drawing has bleached out.

The strips are then developed with developer (A). It is clearly visiblethat the white background of the strips (B) and (C) is less white thanthat of strip (A).

The 2-pyrrolidon(2)yl(1) diazo compound used in the example was preparedas follows: p-aminophenol was brought into reaction with -butyrolactone.Thus 4-pyrrolidon(2)yl(1)phenol was formed, which product was nitratedand then methylated with dimethyl sulfate. The nitro group was reducedto an amino group and the amino group was benzoylated. The4-pyrrolidon(2)yl(l)-2- benzoylaminoanisole was nitrated to4-pyrrolidon(2)yl- (1)-2-benzoylamino-S-nitroanisole, which melts at223- 225 C. Upon reduction, 4-benzoylamino-Z-pyrrolidon-(2)yl(l)-5-methoxyaniline was formed, which product was diazotizecl. Thediazo compound was obtained in the form of the chlorozincate.

EXAMPLE II White base paper of weight 80 g./m. and suitable for thediazotype process is sensitized with a liquid containing:

4 phenyl 2 pyrrolidon(2)yl( l )-5-methoxybenzene diazonium chloride,zinc chloride double salt Tartaric acid 5 Saponin 3 in 1000 ml. of Waterand dried.

The diazotype paper thus obtained contains approxi n1ately 0.45 millimolof diazo compound per m2. A sheet of the diazotype paper is imagewiseexposed underneath a transparent ink drawing until all the diazocompound underneath the image-free portions of the drawing has bleachedout, and is then developed with developer (A).

The copy shows a red image on a bright White background.

When the above-mentioned sensitizing liquid contains, instead of thesaid diazo compound, an equimolar quantity of the diazo compound4-phenyl-2,S-dimethoxybenzene diazonium chloride, zinc chloride doublesalt, the diazotype paper thus obtained is considerably lesslight-sensitive, and gives copies with a black azo-dye-stuff image on abackground having a somewhat dingy stain.

The diazo compound used in the example was prepared as follows:2-hydroxybiphenyl was methylated and then nitrated. The nitro group ofthe 2-methoxy-5-nitrobiphenyl was reduced and the amino group thusobtained was brought into reaction with -butyrolactone. The 2-phenyl-4-pyrrolidon(2)yl(l)anis0le thus prepared was nitrated to 4phenyl-2-pyrrolidon(2)yl(l)-5-methoxynitrobenzene, which melts at 123 C.From this nitro compound the di azo compound was prepared by reductionand diazotization; it was obtained in the form of the chlorozincate.

8 Example III Three sensitizing liquids are prepared: (A) A liquidcontaining:

4 (4 methylphenylthio) 2-pyr rolidon (2 -yl 1 -5-G. methoxybenzenediazonium chloride, zinc chloride double salt 16 Tartaric acid 5 Saponin3 in 1000 ml. of water.

(B) A similar liquid to that mentioned under (A), but containing,instead of the said diazo compound, an equimolar quantity of4-(4-methylphenylthio)-2-Nmethyl-N- ethoxycarbonylamino-S-methoxybenzenediazonium chloride, zinc chloride double salt.

(C) A similar liquid to that mentioned under (A), but containing,instead of the said diazo compound, an equimolar quantity of4-(4-methylphenylthio)-2,5-dimethoxybenzene diazonium chloride, zincchloride double salt.

With each of these liquids a sheet of white base paper of weight g./m.and suitable for the diazotype process is sensitized. Aftersensitization the three sheets are dried. Each sheet containsapproximately 0.37 millimol of diazo compound per m.

A strip of each sheet is imagewise exposed underneath a transparent inkdrawing for the time required to bleach out on the strip of sheet (A),all the diazo compound onderneath the image-free portions of theoriginal. After this, the strips are developed with developer (B).

Strip (A) shows a brown image on a bright white background. Strip (B)shows a dark brown image on a somewhat foggy light brown background.Strip (C) shows a green-black image on a heavily foggy grey background.

A second strip of the sheets (A), (B), and (C), screened from the light,is stored for an hour in a room with a relative humidity of 75% and atemperature of approximately 20 C. The strips are then fed, togetherwith a transparent ink drawing, through a continuously operatingexposure apparatus for the diazotype process with an exposure cylinderof glass which has a surface temperature of approximately 60 C. and inwhich a high-pressure meroury vapour lamp is mounted, with such a speedthat on strip (C) all the diazo compound underneath the imagefreeportions of the drawing has bleached out.

The strips are then developed with developer (B). The white backgroundof the strips (B) and (C) is far less white than that of strip (A).

The diazo compound with the 2-pyrrolidon(2)yl(l) group used in theexample was prepared as follows: 4-pyrrolidon(2)yl(l) 2 nitroanisole wasreduced to 5-pyrrolidon(2)yl(l)-2-methoxyaniline. The amino group wasreplaced according to the Sandmeyer reaction, by a chlorine atom and theproduct thus formed was nitrated. The chlorine atom was subsequentlyreplaced by a p-tolylthio group with the aid of p-tolylmercaptan. The4-p-tolylthio S-methoxy-Z-pyrrolidon(2)yl(l)-nitrobenzene thus obtainedmelts at -l76 C. From this nitro compound the diazonium salt wasobtained in the usual way.

Example IV Paper consisting as to about 50% of synthetic fibres, whichhas been precoated with an aqueous dispersion of non-colloidal silicaand has then been dried, is sensitized with a liquid containing:

4 phenacetylamino 2 pyrrolidon(2)yl(l)-5-(2'- ethylbut)oxy benzenediazonium chloride, zinc chloride double salt 22 Tartaric acid 5 Saponin3 in 1000 ml. of water and dried.

The diazotype paper thus obtained contains approximately 0.37 millimolof diazo compound per 111. The

diazotype paper is imagewise exposed as described in Example II and isthen developed with devoloper (B).

The copy shows a brown image on a non-stained background.

The diazo compound used in the example was prepared as follows:p-aminophenol was brought into reaction with -y-butyrolactone, thennitrated, and alkylated with 2-ethylbutyl bromide to2-nitro-4-pyrrolidon(2)yl(1)(2-ethylbut)oxy benzene. The nitro group wasreduced to an amino group. The latter was acylated wtih phenacetylchloride. The product thus obtained was nitrated to 4-phenacetylamino--(2' ethylbut)oxy-2-pyrrolidon(2)-yl (1)-nitrobenzene,which melts at 148-151 C. From this nitro compound the diazoniumcompound was obtained in the usual way.

Example V A celluloseacetate film layer of Weight approximately 20 g./m.applied on natural tracing paper of Weight about 80 g./m. issuperficially hydrolysed to a depth of about 4 microns and, afterremoval of the chemicals used for the hydrolysis by washing with Water,is sentitized with a solution of The diazotype material thus obtainedcontains approximately 0.95 millimol of diazo compound per 111. Thediazotype material is imagewise exposed as described in Example 11 andis then developed with developer (B).

The copy shows a dark brown image on a clear background.

The diazo compound used in the example was prepared as follows:5-pyrrolidon(2)yl(1)-2-methoxyaniline, HClsalt, was brought intoreaction with dicyanodiamide, after which the biguanidino substituentthus introduced was converted with acetic anhydride into a6-methyl-4,[2]- imino-2,[4]arnino-1H,4H[1H,2H]1,3,5-triazinyl group. Thecompound thus obtained Was nitrated at 4,6'-methyl- 4'-[2'] imino2'[4']-amino-lH,4H[1H,2'H]-1',3',5- triazinyl(l) 2pyrrolidon(2)yl(1)-5-methoxynitrobenzene which melts at 242 C. From thisnitro compound the diazonium salt was obtained in the usual way.

Example VI Transparentized paper (grade 506 from Plastic CoatingCorporation, Massachusetts, USA.) is sensitized with in 1000 ml. ofwater and dried.

The transparent diazotype paper thus obtained contains approximately1.18 millimols of diazo compound per m A sheet of the diazotype paper isimagewise exposed underneath a typed letter until all the diazo compoundunderneath the image-free portions of the letter has bleached out, andis then developed with developer (C).

The copy shows a brown azo-dyestutf image on a nonstained background.The azo-dyestuif image has good absorption for ultra-violet radiation,so that the copy is eminently suitable as an intermediate original formaking further copies on diazotype material.

The diazo compound used in the example was prepared as follows:5-pyrrolidon(2)yl(l)-2-methoxyaniline was 10 brought into reaction withphosgene and then nitrated, in consequence of whichbis-N,N(4-nitro-5-pyrrolidon (2)yl(l)-2-methoxyphenyl)urea was formed,which product melts at 306-307 C. From this bis-nitro compound thebis-diazonium salt was obtained.

Example VII White base paper of weight g./m. and suitable for thediazotype process is sensitized with a liquid containing:

4 diazo 2 methoxy 5 pyrrolidon(2)yl(l)phenylthio-n buty1 ether,chlorozincate g 20 Tartaric acid -g 5 Sodium naphthalene1,3,6-trisulfonate -g 30 Vinnapas H.60 (polyvinyl acetate dispersionfrom Wacker Chemie G.m.b.H., Munich, Germany; Vinnapas is a registeredtrademark) ml 30 in 1000 ml. of water and dried.

The diazotype material thus obtained contains approximately 0.45millimol of diazo compound per m A sheet of the diazotype paper isimagewise exposed underneath a typed letter, until all the diazocompound underneath the image-free portions of the letter has bleachedout, and is then developed with developer (C).

The copy shows a brown image on a bright white background.

The diazo compound used in the example was prepared as follows:p-nitrophenol was chlorinated to 4-nitro-2- chlorophenol. This productwas reduced, brought into reaction with y-butyrolactone, and thenmethylated and nitrated. The2-pyrrolidon(2)yl)(1)-5-methoxy-4-chloronitrobenzene thus obtained wasconverted with butylmercaptan into4-butylthio-5-methoxy-2-pyrrolidon(2)yl (1)-nitrobenzene, which melts at99 C. From this nitro compound the diazonium salt was obtained in theusual way.

Example VIII White base paper of weight 80 g./m. and suitable for thediazotype process is sensitized Wtih a solution of G. Ethane 1,2 dithiolbis -(4' diazo 2' methoxy- 5' pyrrolidon(2)yl(1) phenyl)ether,chlorozincate 25 Tartaric acid 5 Vinnapas H60 30 Sodium naphthalene1,3,6-trisulfonate 30 Example IX White paper of weight g./m. coated onone side with a cellulose acetate film layer (approximately 50% byweight of combined acetic acid) of a thickness of approximately 10microns, Which layer has been afiixed to the paper by means of anadhesive and has been deacetylated to a depth of about 4 microns to anaverage acetyl content, calculated as combined acetic acid, of 20% byweight (which corresponds to an average number of acyl groups at theOH-groups of 0.7), is coated on the deacetylated side of the celluloseacetate layer with a liquid containing:

Titanium dioxide with a particle size of approximately 0.2 micron g 13Hydroxyethylcellulose Cellosize WP-09 (from Union Carbide Corp. of U.S.Ag 27 Glyoxal g 4 Ethanol (96%) ml 8 Water ml 92 and dried at 110 C.during 50 seconds.

The layer thus formed is sensitized with a solution of 25 g. of4-p-tolythi-0-5-methoxy-2-pyrrolidon(2)yl(1)- benzene diazoniumchloride, zinc chloride double salt in 500 ml. of ethanol (96%) and 500m1. of water and dried.

The light-sensitive planographic printing plate thus obtained is exposedunder a positive original until all the diazo compound underneath theimage-free portions of it has bleached out, and the image issubsequently developed by amply wetting the surface of the plate with aliquid which was prepared by dissolving Phloroglucinol 12 Citric acid g11 Concentrated phosphoric acid ml 87 in 950 ml. of Water and bybringing the pH of this solution up to 7 with a sodium hydroxidesolution.

After development, the plate is washed and mounted in an offset printer,upon which prints can at once be made from the plate.

The background of the plate is bright white and does not absorb fattyprinting ink during printing.

Example X White baryta-coated paper is sensitized with a solutioncontaining:

4 benzylthio benzyloxy 2 pyrrolidon(2)yl (l)-benzene diazonium chloride,zinc chloride double salt g 18 Tartaric acid g 5 The aqueous 40%solution of sodium xylene sulfonate Naxonad 4 L (from Nease ChemicalCompany, Lock Haven, Pa., U.S.A.) ml 5 Ethanol (96%) ml 500 Water ml 500and dried.

The diazotype paper thus obtained contains approximately 0.44 millimolof diazo compound per m. A sheet of this paper is imagewise exposed asdescribed in Example II and is developed with developer (A).

The copy shows a very dark violet-brown image on a white background.

The diazo compound used in the example was prepared as follows:4-pyrrolidon(2)yl(1)-2-chlorophenol was benzylated, then nitrated andsubsequently brought into reaction with benzylmercaptan. The4-benzylthio-5- benzyloxy 2 pyrrolidon(2)yl(1) nitrobenzene thusobtained melts at 167 C. From this nitro compound the diazonium salt wasobtained in the usual Way.

Example XI White base paper of weight 80 g./m. and suitable for thediazotype process is coated with a layer by applying approximately g. ofa dispersion containing:

Di(octadecylammonium)oxalate 115 Hydrolysed potato starch, FarinexT.S.D. (from Nationale Zetmeelindustrie N.V., Veendam, Netherlands) Gumarabic 7.5

Oxalic acid, 21-1 0 2.5

12 in 1000 ml. of water and dried.

A light-sensitive layer is formed on the dried layer by applying aliquid containing:

4 methylthio 2 pyrrolidon(2)yl (l) 5 methoxybenzene diazonium chloride,zinc chloride double salt 7 7'-hydroxy-1',2',4,5-naphthimidazole 20Tartaric acid 22.5 Gum arabic 7.5 Farinex T.S. D. 35Di(octadecylammonium)oxalate in 1000 ml. of water and drying.

The diazotype paper thus obtained contains approximately 0.40 millimolof diazo compound per m. A sheet of it is exposed underneath atransparent ink drawing until all the diazo compound underneath theimage-free portions of the drawing has bleached out. The exposed sheetis developed by bringing it into contact with a surface heated to C.

The copy shows a violet-red image on a bright white background.

The diazo compound used in the example was prepared as'follows:

5 pyrrolidon(2)yl(l)-4-nitro-2-methoxychlorobenzene (see Example III)was brought into reaction with methylmercaptan. The4-methylthio-5-methoxy-2-pyrrolidon(2)- yl(l)-nitrobenzene thus obtainedmelts at l37-l38 C. From this nitro compound the diazonium salt wasobtained in the usual way.

Example XII Sized natural tracing paper is sensitized with a solutioncontaining:

4-N-methyl-N-benzoylamino 5 methoxy-2-pyrrolidon(2)yl(1)-benzenediazonium chloride, zinc chloride double salt g 21 Tartaric acid g 5Ethanol (96%) ml 100 Water ml 900 and dried The transparent diazotypepaper thus obtained contains approximately 0.63 millimol of diazocompound per m A sheet of this paper is imagewise exposed as describedin Example I and is then developed with developer (B).

The copy shows a red image on a clear background.

The diazo compound used in the example was prepared as follows:Z-methylamino-4-nitroanisole was converted with benzoyl chloride intoZ-N-methyl-N-benzoylamino-4- nitroanisole. The nitro group of thisproduct was reduced to an amino group, which was brought into reactionwith 'y-butyrolactone. TheZ-N-methyl-N-benzoylamino-4-pyrrolidon-(2)yl(1)-anisole thus obtainedwas nitrated to 4- N-methyl-N-benzoylamino-S-methoxy 2 pyrrolidon(2)yl(1)nitrobenzene, which melts at 137 C. From this nitro compound thediazonium salt was obtained in the usual way.

Example XIII White base paper of Weight 80 g./m. and suitable for thediazotype process is sensitized with a solution of4-(4'-methylphenylthio) 5 (4-chlorophenoxy)-2-pyrrolidon(2)yl(1)-benzene diazonium hydrogen sulfate g 25 Tartaric acidg 5 Vinnapas H. 60 ml 30 in 1000 :ml. of water and dried.

The diazotype material thus obtained contains approximately 0.40millimol of diazo compound per m. A sheet of it is imagewise exposed anddeveloped as described in Example V.

The copy shows a dark brown image on a bright white background.

The diazo compound used in the example was prepared as follows:3,4-dichloronitrobenzene was fused together with p-chlorophenol andpotassium hydroxide. As a result 3-chloro-4-p-chlorophenoxynitrobenzenewas proproduced. This product was reduced and then brought into reactionwith -butyrolactone. The4-p-chlorophenoxy-3-chloropyrrolidon(2)yl(1)-benzene was nitrated andconverted with p-tolylmercaptan into4-p-tolylth-io-5-pchlorophenoxy-Z-pyrrolidon (2 yl( 1 -nitrobenzene,which melts at 140-141" C. From this nitro compound the diazonium saltwas obtained in the usual way.

What I claim is:

1. Diazotype maten'al comprising a support having thereon alight-sensitive layer containing a benzene diazonium salt of the generalformula in which X represents an anion, R represents an alkyl, alkenyl,cycloalkyl, aralkyl or aryl group, and Y represents an acylamino,etherified mercapto or dihydro-1,3,5-triazinyl group, or anon-substituted or alkylor alkoxysubstituted phenyl group.

2. One-component diazotype material according to claim 1, wherein Y is abenzoylamino radical.

3. One-component diazotype material according to claim 1, wherein Yrepresents an alkyl-thio, aralkyl-thio or aryl-thio 'group.

4. A diazo compound of the general formula l r-CH:

in which R represents a non-branched alkyl group having up to 5 carbonatoms, and X represents an anion.

14 5. A diazo compound of the general formula NzX | CHg-CH:

C- Hg R10 II o in which R represents a non-branched alkyl group havingup to 5 carbon atoms, R represents an alkyl group having up to 4 carbonatoms, a benzyl group or a nonsubstituted or alkylor alkoxy-substitutedphenyl group, and X represents an anion.

6. Diazotype material comprising a support having thereon alight-sensitive layer containing a 4-benzoylamino 2 pyrrolidon(2)yl( 1)5 methoxy-benzene diazonium salt.

7. A 4-benzoylamino-2-pyrrolidon(2)yl(1)-5-methoxybenzene diazoniumsalt.

8. Diazotype material comprising a support having thereon alight-sensitive layer containing a 4(4'-methylphenylthio) 2pyrrolidon(2)yl(1)-5-methoxy-benzene diazonium salt.

9. A 4- (4-methylphenylthio -2-pyrrolidon(2)yl( 1 )-5- methoxy-benzenediazonium salt.

References Cited UNITED STATES PATENTS 2,286,701 6/ 1942 Werner 96912,456,514 12/ 1948 Johnston 9691 2,665,985 1/1954 Sus 96--91 3,016,2981/1962 Sanders et al 96--91 XR 3,155,512 11/1964 De Boer 9691 3,338,7138/1967 Hendrickx et al. 96-91 FOREIGN PATENTS 538,869 8/ 1941 GreatBritain.

OTHER REFERENCES Brown, D. J.: Chem. Ind., 22 (1944), pp. 146-148.

NORMAN G. TORCHIN, Primary Examiner. C. L. BOWERS, Assistant Examiner.

